Diazo preparations and process of making same



l aterited Aug, 350, i932 '31P, Q S i 2 Ease extrema @FFHCE.

Halts JOI-INER, 0F BAs-EnswrrzERLane, ASSIGNOE TO THE SOCIETY OF CHEMI-cAL INDUSTRY IN BASLE, or BASEL, SWITZERLAND nlAzo-rsaraaarrons ANDPROCESS OF MAKING SAME no Drawing. Application filed April 29, 1931,Serial No. 533,871, and in Switzerland May 21, 1920.

T he present invention relates to the manufacture of new" diazopreparations. It com prises the process of making these preparations, aswell as the new preparations them selves. The diazo-compounds of theamino-derivatives of diarylethers of the general formula I NHz whereinthe two benzene nuclei may carry substituents, have acquired importancein the production of fast tints on the fibre. Particularly valuableamong these are those which correspond with the general formula NHawherein m stands for halogen and y for by drogen, alkyl, O-alkyl orhalogen. The diazotization of these derivatives, however, offers certaindiiiiculties, so that the products must which always. contains aconsiderable excess" of free mineral acid.

If necessary, the diazo-compound may be salted out by means of an easilysoluble salt, preferably of the mineral acid in question.

The new diazo-hydrochlorides form yellow crystalline powders andcorrespond very probably with the general formula wherein a: stands forahalogen atom and y for hydrogen, alkyl, O-alkyl or halogen, or

quite generally with the general formula NHz wherein the two benzenenuclei may carry substituents.

The following examples illustrate the invention r Ewample 1 220 parts byweight of 4c-chloro-2-aminodiphenylether are finely powdered, sifted andcautious addition of chalk (about 25 parts by weight) and thehydrochloride of the 4- chloro-2-diazo-l-diphenylether of the probableformula i l is salted out by addition of 200 parts by weight ofmagnesium chloride. This hydrochloride forms beautiful yellow crystalsand The filtered diazo-solution is now neutralized byit is obtainedingood yield. It can easily be filtered or centrifuged and then dried ata low 7 temperature; It can, however, before being dried, and thereforein still moistcondition,

V be mixed with the usual dyeing auxiliaries or with any suitablediluent, whereby its explosiveness (which indeed is not 7 very great)maybe essentially diminished. The

yellow crystals of the hydrochloride are remarkably freely soluble inwater to a neutral solution. f p p a In like manner the-process can beconducted Withother diazo-compounds of the diarylethers or with othermineral acids.

EammpZaZJ y adding chalk in portions, filtered once more, if necessary,and the diazonium chloride of the probable formula V v OOOH: N-Ol i lll1 is then separated by-addition of easily soluble chlorides, suchas,-for example, 20 parts of magnesium chloride, and of 20 parts ofanhydrous calcium chloride. On standing in the cold thejd-iazoniumchloride-separates in the form of large, yellow crystals.

-. 1n this -and; ;in the preced ng examplethe chalk maybe replaced byother suitable new, tralizing agents, such as calcium bicarbonate,

magnesium carbonate, aluminium oxide. Crystalline separations may alsobe obtained after neutralizing the acid in excess, if the. diazotizationis carired out with sulfuric acid or phosphoric; acid instead of withhydrochloric acid.

' In like manner the process is conducted with other aminodiarylethersof the above A x j statedrgeneral:formula, for example those 'in whichmstands for bromine or iodine, or

in which besides m other substituents are presentrinthe 'arylnucleus,-.such as, for example,

a further halogen atom, or thoseinwhich y stands'for OCHQ, OG H Cl orBr,such 'as, for example l-bromo 2-'aminodiphenyl- 4:: 54-trichloro-2-aminodiphenylether,

ether, 4: 5-dichloro 2 aminodiphenylether, or

' also ortho-aminodiphenylether, ortho-amino-J-chlorodiphenylether,ortho-aminoy-methoxydiphenylether, ortho-amino-24J-di chlov rodiphenylether, ortho-aminof2'-chlorodiphenylether,ortho-amino 5 -nitrodiphenylproperties. p I I Instead ofthea-naphthylamide, any other coupling component can be used, such as,

hydrochlorides of wherein y stands ether, ortho-amino-5-nitro-4:4-dichloro di phenylether, ortho-amino-5-nitro-4-chlorodiphenylether,ortho-aminoA-benzoylamin diphenylether,ortho-amino-t-ethylsulfonodiphenylether, sulfamide-diphenylether.

Example 5 Cotton is padded in known manner with a solution of 12 gramsof the -naphthylamide ortho-a1nino-4-ethylphenylof 2: 3-hydroxynaphthoicacid and then dc Velop'ed with a solution containing per litre 50 gramsof the preparation made as described in the preceding example andcorresponding with about 20 percent. of base, and

' i .10 cc.,of acetic acid of per cent. strength.

Red tints are obtained of the known good among others, the anilide,para-chloranilide, V

,B-Inaphthylamide of Y2: 3-hydroxynaphthoic acid; also1-hydroxynaphthalenelrphenylketone, aceto acetic acid arylides, such asdiaceto-acetic acid-ortho-tolidide further, in

stead of the product of Example 1 other preparations made according tothis inven tion can be used. What I claim isl: V 1 v 1. As new productsthe solid diazonium the generalformula time;

for hydrogen or methyl.

2. As a new product the solid diazonium hydrochloride of the formula 3.As a new product the solid diazonium hydrochloride 'of'the formula v iIn witness whereof I have hereunto signed} my name this '21stday ofApril, 1931. I V HANS JOHNER.

